Peroxydisulfate-based advanced oxidation process has drawn increasing interest recently. Quenching the residual peroxydisulfate is essential for the accurate measurement of the concentration of target pollutants. However, it was rarely discussed which reductant is best for peroxydisulfate quenching. In this study, how the quenching of peroxydisulfate by four commonly used quenchers (methanol, ascorbic acid, sodium thiosulfate and sodium sulfite) affected the concentration of carbamazepine was investigated. Sodium sulfite reacted with carbamazepine directly, with the highest removal rate up to 39%. Higher carbamazepine removal rate was achieved by peroxydisulfate/sodium sulfite than by sodium sulfite alone. SO3•− and SO5•− rather than SO4•− played the major role in carbamazepine removal by sodium sulfite or peroxydisulfate/sodium sulfite. Methanol was found unable to reduce peroxydisulfate. Ascorbic acid, when used with a concentration more than three times higher than that of peroxydisulfate, was the best quencher with the lowest carbamazepine removal rate observed at a pH range of 3.5–10.0. Sodium thiosulfate was unfit for peroxydisulfate quenching at pH 3.5 as it was decomposed and formed bisulfite under strong acidic condition. The results of this study provided valuable guidance to the selection of proper quenchers for peroxydisulfate-related advanced oxidation processes.